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Ok I know the tail has its own brain but all of the 3 faces have different/change facial expressions so does each face have a brain behind it or is there only one brain which controls all three? I just have to know

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As far as I know, this has never been explained. However, we may be able to make some inferences.

Doduo and Dodrio, both multi-headed Pokemon connected by one body, have separate brains for each head.

Zweilous also has one brain per head, evidenced by the fact the two get in disputes constantly.

As Weezing is essentially two Koffings, one can assume that they also have two brains.

Do you see a pattern here? All these multi-headed Pokemon each have a brain per head. Therefore, it can be safely assumed that each Alolan Exeggutor head has its own brain.

Hope I helped!

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Actually, Hydreigon's secondary heads lack any brains.
Yeah, just realized that. Edited out to just Zweilous.
Thank you! Fairly new to Pokemon and have only watched sun and moon so this has helped a lot!
No problem! If it helped, could you please click the green checkmark in the top right of my answer?